US4870113A - Rigid polyphosphazene foam and process for making same - Google Patents

Rigid polyphosphazene foam and process for making same Download PDF

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Publication number
US4870113A
US4870113A US07/290,501 US29050188A US4870113A US 4870113 A US4870113 A US 4870113A US 29050188 A US29050188 A US 29050188A US 4870113 A US4870113 A US 4870113A
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United States
Prior art keywords
composition
polyphosphazene
foamed
blowing agent
sup
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Expired - Fee Related
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US07/290,501
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English (en)
Inventor
Warren B. Mueller
Susan D. Landry
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Ethyl Corp
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Ethyl Corp
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Priority to US07/290,501 priority Critical patent/US4870113A/en
Assigned to ETHYL CORPORATION reassignment ETHYL CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: LANDRY, SUSAN D., MUELLER, WARREN B.
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Publication of US4870113A publication Critical patent/US4870113A/en
Priority to CA002004152A priority patent/CA2004152A1/fr
Priority to AU45990/89A priority patent/AU4599089A/en
Priority to JP1334663A priority patent/JPH02225538A/ja
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2385/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers
    • C08J2385/02—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers containing phosphorus
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/05—Use of one or more blowing agents together
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S521/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S521/918—Physical aftertreatment of a cellular product

Definitions

  • Cellular plastics have been available for many years.
  • One of the first of such materials was cellular rubber dating to the 1910-1920 period.
  • cellular compositions were made from latex, phenol-formaldehyde resins, urea-formaldehyde resins, PVC, polyurethane, cellulose acetate, polystyrene, polyethylene, epoxides, ABS resins, silicones and very recently polyphosphazenes.
  • Polyphosphazene foams have very desirable properties in that they are highly fire resistant and when subjected to direct flame do not produce toxic smoke which is encountered with many other common foamed materials, notably, polyurethanes.
  • Polyphosphazenes are polymers containing a plurality of ##STR1## groups wherein substituents are bonded to phosphorus.
  • the polyphosphazenes which are the concern of this invention are high molecular weight linear polyphosphazenes containing 50 or more of the above units and having molecular weights from about 10,000 up to about 5,000,000 or higher. They are substantially linear and have little, if any, cross-linking. In general, they are soluble in benzene, toluene, cyclohexane and tetrahydrofuran and are relatively insoluble in linear aliphatic hydrocarbons such as hexane or heptane.
  • Groups substituted on phosphorus include phenoxy, alkylphenoxy, alkoxyphenoxy, aminoalkylphenoxy, alkylaminoalkylphenoxy, dialkylaminoalkylphenoxy, halophenoxy (e.g., para-chlorophenoxy, meta-bromophenoxy, trifluorophenoxy and the like), haloalkylphenoxy (e.g., trifluoromethylphenoxy), alkoxy, haloalkoxy (e.g., trifluoroethoxy), alkenylphenoxy (e.g., ortho-allylphenoxy and the like).
  • halophenoxy e.g., para-chlorophenoxy, meta-bromophenoxy, trifluorophenoxy and the like
  • haloalkylphenoxy e.g., trifluoromethylphenoxy
  • alkoxy haloalkoxy (e.g., trifluoroethoxy)
  • alkenylphenoxy
  • foams are made by mixing the polyphosphazene gum, a blowing agent and a peroxide or sulfur-type curing agent and heating the blended components to activate the blowing agent and cure the resultant foam.
  • a flexible elastomeric polyphosphazene foam is first made by forming a composition comprising a substantially linear high molecular weight polyphosphazene gum, a curing agent, a blowing agent and optionally a plasticizer, an inorganic filler, an accelerator and processing aids.
  • the composition is masticated or mixed until it forms a substantially homogeneous blend whereupon mixing is stopped.
  • the resultant composition is shaped into conventional slabs or sheets or is extruded into a hollow cylindrical form prior to curing and then heated in an unconfined environment to a temperature which activates the blowing agent causing the composition to expand into a foamed composition and completing the cure of the foamed composition to produce a flexible elastomeric foamed polyphosphazene composition.
  • the shaped composition can be pre-cured prior to curing. That is, the shaped composition or homogenous blend can be aged at a temperature above the predetermined maximum mixing temperature but below the activation temperature of the blowing agent. This operation causes a limited amount of cross-linking to occur raising the viscosity of the composition such that the blowing gas does not escape during the blowing operation.
  • This step is usually done in a pre-cure oven.
  • the foamed material is flexible, it can easily be re-shaped into a variety of configurations and designs and processed into a rigid foam having a specific shape by heating the shaped flexible polyphosphazene foamed material to a temperature and for a length of time sufficient to cause the shaped flexible composition to become rigid.
  • rigid foamed sheets, slabs, pipes and the like having varying degrees of curvature or complex contours possessing excellent compression resistant and flammability properties can be produced.
  • a preferred embodiment of the invention is a process for making a low density rigid polyphosphazene foam having excellent flammability and compression resistant properties, said process comprising:
  • composition comprising a substantially linear high molecular weight polyphosphazene gum, a curing agent, a blowing agent and optionally a plasticizer, an inorganic filler, an accelerator and processing aids,
  • Another embodiment of the invention is a low density foamed shaped rigid polyphosphazene composition made by a process comprising:
  • composition comprising a substantially linear high molecular weight polyphosphazene gum, a curing agent, a blowing agent and optionally a plasticizer, an inorganic filler, an accelerator and processing aids,
  • High molecular weight linear polyphosphazenes are known polymers. Their preparation is described in the literature and in patents such as U.S. Pat. Nos. 3,515,688; 3,700,629; 3,702,833; 3,838,073; 3,843,596, 3,844,983, 3,853,794; 3,883,451; 3,888,799; 3,888,800; 3,896,058; 3,943,088; 3,948,820; 3,970,533; 3,972,841; 3,994,838; 4,006,125; 4,116,785; 4,123,503; 4,128,710 and 4,129,529.
  • linear polyphosphazenes consist essentially of ##STR2## in which n can range from about 50 to 50,000 or more and wherein any of a large number of groups can be substituted on phosphorus.
  • Substituent groups can include alkoxy, substituted alkoxy such as haloalkoxy or alkoxyalkoxy, aryloxy, substituted aryloxy wherein the substituents can be alkyl, alkoxy, halo, alkenyl, haloalkyl, amino, alkylamino, dialkylamino and the like.
  • Other phosphorus substituents can be halogen (e.g., chlorine), alkenoxy and the like.
  • the polyphosphazene gum is first blended with other ingredients to give a formulation.
  • An essential component of the formulation is a blowing agent.
  • the amount of blowing agent should be that which will evolve sufficient gas to give a foam of the desired density but not an excessive amount which results in splitting of the foam.
  • Blowing agents decompose to evolve gas upon heating. This decomposition temperature varies over a wide range with different foaming agents.
  • Many foaming agents are azo compounds which evolve nitrogen when undergoing thermal decomposition.
  • blowing agents include dinitrosopentamethylenetetramine, 4,4'-oxybis(benzenesulfonyl hydrazide), axodicarbonamide, ammonium carbonate, ammonium bicarbonate, sodium bicarbonate, ammonium nitrite, tertbutylamine nitrite, guanidine nitrite, guanylurea nitrite, sodium borohydride, potassium borohydride, urea, biuret, N-nitro urea, diazomaniobenzene, 2,2'-azobis(2-methylpropionitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobiscyclohexanecarbonitrile, azobisisobutyramidoxime, azobisformamide, N,N'-di-tert-butylazobisformamide, N,N'-diphenylazobisformamide, phenylhydrazine, benzylmonohydro
  • Curing agents encompass a broad range of compounds which serve to promote cross-linking of the polyphosphazene.
  • One class of curing agents is made up of peroxides.
  • the most important curing agent used to make the present foamed compositions are the sulfur-type curing agents generally referred to as vulcanizing agents.
  • a typical sulfur vulcanizing system comprises sulfur, an accelerator and promoters. Zinc oxide is usually included with the sulfur.
  • Other accelerators include zinc dialkyldithiocarbamates (e.g., zinc dimethyldithiocarbamate, zinc dibutyldithiocarbamate and the like).
  • Other useful accelerators are zinc benzothiazylsulfide, N-cyclohexyl-2-benzothiazylsulfenamide, 4,4'-dithiomorpholine, fatty acids in combination with zinc oxide such as stearic acid, zinc fatty acid salts such as zinc stearate, tetraalkylthiuram monosulfide, tetraalkylthiuram disulfide, 2-benzothiazoyl disulfide, zinc benzothiazolyl mercapto, mercaptobenzothiazole, 2-benzothiazolysulfenamide, amines, diphenyl guanidine, thiobisamines and the like.
  • filler Another component that is usually included in polymer foam compositions is a filler. These are usually inorganic materials although some organic materials are used. Examples of fillers are clay, talc, mica asbestos, feldspar, bentonite, wollastonite, fullers earth, pumice, pyrophillite, rottenstone, slate flour, vermicullite, calcium silicate, magnesium silicate, alumina, hydrated alumina, antimony oxide, magnesia, titania, zinc oxide, silica, calcium carbonate, barium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, lime, magnesium hydroxide, carbon black, graphite, metal powders, fibers and whiskers, barium ferrite, magnetite, molybdenum disulfide, glass fibers or flakes, ground glass and the like.
  • the polyphosphazene formulations which are foamed according to the present invention generally include a plasticizer. These can be liquids which when blended with the polyphosphazene gum and the other components tend to reduce the viscosity of the mass and assist in making a homogenous blend.
  • plasticizers include tricresylphosphate, triphenylphosphate, cresyldiphenylphosphate, butyl octyl phthalte, dibutyl phthalate, dicyclohexyl phthalate, diisodecyl phthalate, di-2-ethylhexyl phthalate, ditridecyl phthalate, isooctylisodecyl phthalate, diisodecyl adipate, di-2-ethylhexyl adipate, octyldecyl adipate, diisobutyl adipate, diisooctyl adipate, di-2-ethylhexyl azelate, diisodecyl azelate, dibutyl maleate, glycerol ricinoleate, isopropyl myristate, isopropyl palmitate, butyl maleate
  • the amount of the different components in the formulation can vary widely based upon parts by weight per 100 parts by weight of polyphosphazene gum. A useful range is given in the following table:
  • the components in the formulated compositions are then subjected to mechanical mixing or mastication to form a substantially uniform blend.
  • This mixing is conducted in the same type equipment used in compounding rubber prior to vulcanization. Suitable mixing equipment on the laboratory scale is marketed under the trademark “Brabender”. Larger mixing equipment is marketed under the “Banbury” trademark.
  • Brabender Larger mixing equipment is marketed under the “Banbury” trademark.
  • the composition can be shaped into useful forms such as sheets and slabs for use in insulation or cushions, or it can also be extruded into hollow cylindrical forms for use as pipe insulation.
  • the shaped composition Prior to curing, the shaped composition optionally can be aged at a temperature above the pre-determined maximum mixing temperature but below the activation temperature of the blowing agent. This operation causes a limited amount of cross-linking to occur raising the viscosity of the composition such that the blowing gas does not escape during the blowing operation. This step is usually done in a pre-cure oven. Good results have been achieved when the shaped composition is maintained at a pre-cure temperature of about 100°-20° C. for a period of about 5-20 minutes.
  • the shaped pre-cured composition is heated in an unconfined environment high enough to activate the blowing agent.
  • the composition then expands forming a flexible cellular polyphosphazene article.
  • unconfined environment means that there is space available into which the shaped polyphosphazen composition can expand during cell development. As it reaches its final volume it may again be confined in some form or mold.
  • the cellular polyphosphazene article can be re-shaped into a variety of geometrical forms and configurations prior to its conversion to a rigid polyphosphazene material.
  • flexible hollow cylindrical tubes can be re-shaped into tubes having varying degrees of curvature or bend or complex contours such as "S" or "L” configurations and the like and processed into rigid tubes of the same configuration or design and used as insulation for pipes of the same shape.
  • the shaped flexible elastomeric foamed polyphosphazene is heated to a temperature and for a length of time which is sufficient to transform the flexible, shaped cellular polyphosphazene into a rigid foamed composition of the same shape as the flexible composition.
  • Heating can be effected, for example, by radiation heating (e.g., infra-red or microwave) or by convection heating. Suitable temperatures range from about 75° to 600° C., more preferably 100° to 300° C. with useful heating times varying from about 10 minutes to 25 days, preferably 8 to 24 hours. The time and temperature can be adjusted depending on the geometry and thickness of the flexible article, the degree of rigidity desired and the heating mode. Excellent results have been achieved when the shaped flexible elastomeric polyphosphazene composition is heated to a temperature of about 200° C. for a period of time of about 16 hours.
  • radiation heating e.g., infra-red or microwave
  • convection heating effected, for example, by convection heating. Suitable temperatures range from about 75° to 600° C., more preferably 100° to 300° C. with useful heating times varying from about 10 minutes to 25 days, preferably 8 to 24 hours.
  • the time and temperature can be adjusted depending on the geometry and thickness of the flexible
  • another embodiment of the present invention is a shaped article made from a rigid foamed polyphosphazene composition made by the process of the present invention.
  • the polyphosphazene gum was a high molecular weight linear polymer substituted with about 52 mole percent phenoxy, 42 mole percent p-ethylphenoxy and 6 mole percent o-allylphenoxy groups.
  • the components were blended in a Banbury mixer until a substantially homogeneous blend was obtained.
  • a curing concentrate was separately formulated as follows:
  • the above concentrate was mixed in a Banbury mixer at 60 rpm and then in a 2-roll mill. Finally, the first formulation above was placed on one roll of a 2-roll mill and 14.9 parts by weight of the concentrate were randomly dropped into the nip of the 2-roll mill as the blend rotated on one roll. The blend was then cut from the roll and was homogenized by 20 passes through the mill with folding after each pass to form a sheet. The sheet was cut to form a rectangular slab which was placed in a mold. The mold was placed in a pre-cure oven maintained at 103.3° C. which is below the activation temperature of the blowing agent for approximately seventeen minutes and placed in a foaming oven for a twenty-five minute period. The foaming oven was maintained at 160° C.
  • test specimens were prepared from the foam and foam quality, water absorption, compression resistance, density, water vapor permeability, tensile strength, and flexural modulus measurements were obtained on the test specimens. The results are shown in the following Table 1.
  • Flammability properties were also measured for the rigid polyphosphazene foam prepared as described above by measuring test specimens of the foam for acid gas generation, flame spread index, thermal conductivity, specific optical density, rate of heat release and limiting oxygen index. The results are shown in the following Table 2.
  • another feature of the present process is that it permits the formation of joint bonds between two or more individual pieces of flexible foam so that when the individual pieces of flexible foam are converted to a rigid foam by the process of the invention, they bond with one another to form a single unitary composite piece of rigid material.
  • the edges of two or more separate pieces of flexible foam can be abutted against each other and heated in accordance with the process of the invention and converted to a unitary composite piece of rigid foam.
  • a bond forms between the individual pieces of the flexible foam where the edges of the pieces contact one another and a single, unitary composite piece of rigid foam is produced thereby.
  • the present process also can be used to bond two pieces of flexible foam together each having a cut edge with a 45 degree angle to produce a 90 degree piece of rigid foam.
  • This feature of the invention virtually eliminates or reduces the need for the use of conventional adhesives such as solvent-dispersed synthetic rubber resin adhesives to bond separate pieces of foamed materials together which often contribute to smoke generation in a fire situation.
  • the tensile strength of a bonded piece of rigid foam was measured and compared to that of a single non-bonded piece of rigid foam.
  • An identical formulation as previously described was prepared, placed in a mixing chamber and mixed until a substantially homogeneous blend was obtained.
  • the blended formulation was removed from the mixer and passed between the rolls of a two-roll mill about 20 passes with folding between passes to form a 0.5 cm sheet.
  • the sheet was cut to form a rectangular slab which was placed in a mold.
  • the mold was placed in a pre-cure oven maintained at 103.3° C. which is below the activation temperature of the blowing agent.
  • the slab was then removed from the mold and placed in a foaming oven for a twenty-five minute period.
  • the foaming oven was maintained at 177° C. which is above the activation temperature of the foaming agent.
  • Two strips were cut from the foamed flexible composition each 2.5 inches in length, 0.2 inch in thickness and 1 inch wide and placed end to end with the two ends of the strip touching each other. The strips were then placed in an air circulation oven, heated to 200° C. and maintained at that temperature for 16 hours to convert the individual pieces of flexible foam to a solitary composite rigid foam.
  • the sample was taken out of the oven, allowed to cool to ambient temperature where adhesion between the two foamed pieces was observed to be very good.
  • the tensile strength of the bonded piece of rigid foam was measured by the ASTM D 412 method and found to be approximately 17 psi which is about the same as the tensile strength of the non-bonded rigid foam test specimen reported in Table 1 above.
  • another embodiment of the present invention is a method of bonding one piece of cured flexible foamed polyphosphazene elastomer material to at least one other piece of cured flexible foamed polyphosphazene elastomer material to form a single unitary piece of rigid foamed polyphosphazene composite material said process comprising placing said pieces of cured flexible foamed polyphosphazene elastomer material in juxtaposition with and abutting one another and heating said pieces at a temperature and for a length of time sufficient to cause said pieces to bond together and form a single unitary piece of rigid foamed polyphosphazene composite.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Molding Of Porous Articles (AREA)
US07/290,501 1988-12-23 1988-12-23 Rigid polyphosphazene foam and process for making same Expired - Fee Related US4870113A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US07/290,501 US4870113A (en) 1988-12-23 1988-12-23 Rigid polyphosphazene foam and process for making same
CA002004152A CA2004152A1 (fr) 1988-12-23 1989-11-29 Mousse de polyphosphazene rigide et procede de production connexe
AU45990/89A AU4599089A (en) 1988-12-23 1989-12-06 Rigid polyphosphazene foam and process for making same
JP1334663A JPH02225538A (ja) 1988-12-23 1989-12-22 硬質ポリホスフアゼン発泡体及びその製造方法

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JP (1) JPH02225538A (fr)
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Cited By (4)

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Publication number Priority date Publication date Assignee Title
US4948648A (en) * 1989-12-11 1990-08-14 Ethyl Corporation Fire resistant laminar cushioning material
US5075028A (en) * 1989-11-13 1991-12-24 Copolymer Rubber & Chemical Corp. Accelerator compositions
US5147904A (en) * 1989-08-24 1992-09-15 Thera Patent Gmbh & Co. Kg Open-pored moldings, a process for their production and use thereof
CN116162440A (zh) * 2022-12-08 2023-05-26 西安近代化学研究所 一种聚磷腈橡胶与金属粘接用底涂胶、制备方法及应用

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Publication number Priority date Publication date Assignee Title
WO1993005103A1 (fr) * 1991-09-03 1993-03-18 Terence Allan Russell Structures de renforcement

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Cited By (5)

* Cited by examiner, † Cited by third party
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US5147904A (en) * 1989-08-24 1992-09-15 Thera Patent Gmbh & Co. Kg Open-pored moldings, a process for their production and use thereof
US5075028A (en) * 1989-11-13 1991-12-24 Copolymer Rubber & Chemical Corp. Accelerator compositions
US5354793A (en) * 1989-11-13 1994-10-11 Dsm Copolymer, Inc. Accelerator compositions and rubber compounding composition embodying the same
US4948648A (en) * 1989-12-11 1990-08-14 Ethyl Corporation Fire resistant laminar cushioning material
CN116162440A (zh) * 2022-12-08 2023-05-26 西安近代化学研究所 一种聚磷腈橡胶与金属粘接用底涂胶、制备方法及应用

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JPH02225538A (ja) 1990-09-07
CA2004152A1 (fr) 1990-06-23

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